CN1225745C - Proton conducting material and method for preparing the same, and electrochemical device using the same - Google Patents

Proton conducting material and method for preparing the same, and electrochemical device using the same Download PDF

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Publication number
CN1225745C
CN1225745C CNB008105561A CN00810556A CN1225745C CN 1225745 C CN1225745 C CN 1225745C CN B008105561 A CNB008105561 A CN B008105561A CN 00810556 A CN00810556 A CN 00810556A CN 1225745 C CN1225745 C CN 1225745C
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proton
proton conductor
group
carbon
fullerene
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CN1361916A (en
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日隈弘一郎
B·皮特扎克
C·罗斯特
阿多诚文
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Sony Corp
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Sony Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

A proton conducting material which comprises a base material comprising a carbonaceous material having carbon as a main component and, introduced into the base material, a group capable of dissociating a proton. In the proton conducting material, a proton moves via the group capable of dissociating a proton, and the conductivity for anion is greater than that for an electron. As the carbonaceous material, use is made of a carbon cluster such as a fullerene and a tubular carbon (so-called carbon nano-tube), a carbonaceous material having a diamond structure and the like.

Description

The electrochemical appliance of proton conductor and production method thereof and this proton conductor of use
Technical field
The present invention relates to a kind of proton (H +) conductor and production method thereof and use the electrochemical appliance of this proton conductor.
Background technology
In recent years, as the solid polyelectrolyte type fuel cell that is used for electric automobile, known use has the polymeric material of proton (hydrionic) conductivity, as perfluorosulfonic acid ester resin (for example, the Nafion_ of Du Pont company production).
As newer proton conductor, also cicada contains the polymolybdote of a large amount of hydrate waters, as H 3Mo 12PO 4029H 2O, or contain the oxide of a large amount of hydrate waters, as Sb 2O 65.4H 2O.If above-mentioned polymeric material and hydrated compound are in wet state, under the temperature near normal temperature, each all shows high proton electrical conductance.
For example, even perfluorosulfonic acid ester resin also shows the reason of very high proton electrical conductance at normal temperatures, the moisture that has existed in a large number from the proton of the sulphonate-base ionization of resin and polymer substrate combine (hydrogen bond in conjunction with), the water of generation protonation, i.e. oxonium ion (H 3O+), the proton of oxonium ion form can migration smoothly in polymer substrate.
Recently, electrical conduction mechanism and the diverse a kind of proton conductor of above-mentioned every kind of proton conductor have also been developed.
That is to say, had been found that a kind of composite metal oxide, as the SrCeO of Yb doping with perovskite structure 3, show proton conductive, and do not use moisture as the migration medium.The electrical conduction mechanism of this composite metal oxide is considered to, conduction when proton conducts between the oxonium ion that forms the perovskite structure skeleton one by one.
Yet, the proton of conduction did not exist in composite metal oxide originally, but produce by following mechanism: promptly, when the steam that contains in perovskite structure and the environmental gas contacts, the hydrone of high temperature and the anoxic partial reaction that forms in perovskite structure by Yb doping etc. produce proton.
Yet there is following point in above-mentioned various proton conductors.
In order to keep high proton conductivity, in use, host material as above-mentioned perfluorosulfonic acid ester resin, must be placed under the enough wet state continuously.
Therefore, the humidifier of structural requirement and the various annex of system's (for example using the fuel cell of this host material), thus produced the problem that enlarges system scale and improve system cost.
Use the system of host material to also have the another one problem, promptly operating temperature range must limit, in case contained humidity freezes or seethes with excitement in the matrix.
Composite metal oxide with perovskite structure has a problem, and promptly operating temperature must remain under 500 ℃ or the higher high temperature, to guarantee effective proton conductive.
Like this, all there are some problems in the proton conductor of correlation technique, and promptly the performance of every kind of conductor is to the dependence height of atmosphere, more specifically, must provide aqueous vapor or steam, to guarantee the performance of conductor to conductor, in addition, the operating temperature of conductor is too high or operating temperature range is restricted.
Content of the present invention
First purpose of the present invention provides a kind of can the use and the low proton conductor of atmosphere dependence in comprising the wide temperature range of normal temperature, promptly no matter whether moisture is the migration medium, and it does not need moisture; A kind of method of producing this proton conductor is provided; And provide a kind of electrochemical appliance that uses this proton conductor.
Second purpose of the present invention provides a kind of proton conductor, when keeping above-mentioned performance, present a kind of film and form ability, thereby can use with the form of high-strength thin-film, present saturating property of gas barrier or air impermeability, with good proton conductive, a kind of method of producing this proton conductor is provided, and a kind of electrochemical appliance that uses this proton conductor is provided.
The invention provides a kind of proton conductor, comprise a kind of carbonaceous material that mainly contains carbon, to wherein introducing the proton dissociation group.
The present invention also provides a kind of method of producing this proton conductor, comprises the step of introducing the proton dissociation group in the carbonaceous material that mainly contains carbon.
The present invention also provides a kind of electrochemical appliance, comprises first kind of electrode, second kind of electrode and the proton conductor between first kind and second kind of electrode, and this proton conductor comprises the carbonaceous material that mainly contains carbon, to wherein having introduced the proton dissociation group.
According to proton conductor of the present invention, because described conductor mainly comprises the carbonaceous material with proton dissociating power, even under drying regime, proton is also transmitted easily or is conducted, and proton can (at least in about 160 ℃ of-40 ℃ of scopes) show high conductivity in comprising the wide temperature range of normal temperature.Though proton conductor of the present invention even also have enough proton conductives under drying regime, it also can have proton conductive under dampness.Moisture can be from the outside.
According to electrochemical appliance of the present invention, because proton conductor remains between first kind and the second kind of electrode, so this electrochemical appliance can be exempted the needs to humidifier etc., and that humidifier etc. are requirement moisture is necessary with the known fuel that improves proton conductive as the migration medium.So apparatus structure of the present invention has favourable littler, simpler structure.
The accompanying drawing summary
Figure 1A and 1B are the figure of expression as the structure of the polyhydroxylated fullerene molecule of an example of fullerene of the present invention (fullerene) derivative;
Fig. 2 A, 2B and 2C show the fullerene derivate embodiment that introduces the proton dissociation group.
The embodiment of Fig. 3 A and 3B explanation fullerene molecule;
Fig. 4 is illustrated in the embodiment of the carbon that mainly comprises in the proton conductor of the present invention bunch;
Fig. 5 represents to have other embodiment of the carbon bunch of part fullerene structure;
Fig. 6 represents to have other embodiment of the carbon bunch of diamond lattic structure;
Fig. 7 represents the additional embodiment of the carbon that mutually combines bunch;
Fig. 8 is the schematic diagram of a kind of embodiment of proton conductor of the present invention;
Fig. 9 is the schematic configuration diagram of a kind of fuel cell of expression;
Figure 10 is the schematic configuration diagram of hydrogen-air cell;
Figure 11 is a kind of schematic configuration diagram of electrochemical appliance;
Figure 12 is the schematic configuration diagram of another kind of electrochemical appliance;
Figure 13 A and 13B respectively represent the embodiment as the tubulose carbonaceous material of the present invention of the base material of proton conductor of the present invention or raw material;
Figure 14 shows tubulose carbonaceous material derivative of the present invention;
Figure 15 is the schematic diagram of tubulose carbonaceous material derivative;
Figure 16 is the schematic diagram of another kind of tubulose carbonaceous material;
Figure 17 A and 17B are the figure that tests the equivalent electric circuit of disk (pellet) in the expression embodiments of the invention;
Figure 18 is the figure that the result of disk complex impedance is measured in expression;
Figure 19 is the temperature dependent figure of the proton conductive of expression disk;
Figure 20 is illustrated in the figure that uses the generator experimental result of fullerene derivate in the embodiments of the invention 1;
Figure 21 is the figure that the complex impedance result of disk in the embodiments of the invention 4 and the disk among the comparative example 2 is measured in expression;
Figure 22 is the temperature dependent figure of the proton conductive of expression disk;
Figure 23 is illustrated in to use the figure of carbon electrode by the TOF-MS spectrum of the carbon dust of arc discharge method production in the embodiments of the invention 8; With
Figure 24 is the figure that is illustrated in film complex impedance measurement used in the embodiments of the invention that wherein use the tubulose carbonaceous material.
Implement best mode of the present invention
Hereinafter, the method for using proton conductor of the present invention and producing this proton conductor being described in detail with reference to the attached drawings, and the electrochemical device that uses this proton conductor.
Proton conductor according to a kind of embodiment of the present invention mainly comprises to the carbonaceous material that mainly contains carbon of wherein introducing the proton dissociation group.In this manual, " disassociation of proton (H+) " refers to " proton dissociates from functional group by ionization ", and " proton dissociation group " refers to " functional group that dissociates proton by ionization energy ".
In this proton conductor, proton moves between the proton dissociation group, presents ionic conductivity.
As fullerene derivate, can use any suitable material, as long as it mainly is made up of carbon.But after introducing the proton dissociation group, ionic conductance is essential greater than electronic conductance.
Be as the carbon of carbon atom aggregation bunch and comprise the carbonaceous material of diamond lattic structure as what the fullerene derivate of matrix fullerene derivate can specifically be enumerated.
Many kinds of carbon bunch are arranged.Certainly, fullerene, at least its part the fullerene structure of open end and tubular carbonaceous material or so-called carbon nano-tube are arranged is preferred.
Certainly, these materials only are illustrative, because the ionic conductance behind any satisfied introducing proton dissociation group all is available greater than the material of the above-mentioned condition of electronic conductance.
Below, explain that the present invention uses for some typical cases of representational carbonaceous material.
At first, explain with the embodiment of fullerene as carbonaceous material.
According to this embodiment, the not restriction especially of fullerene derivate molecular species as to the fullerene derivate base material of wherein introducing the proton dissociation group as long as in fullerene molecule is characterized as spherical carbon bunch scope, generally comprises C 36, C 60(seeing Fig. 3 A), C 70(seeing Fig. 3 B), C 76, C 78, C 80, C 82And C 84Fullerene molecule.The mixture that should be noted that these fullerene molecules or other similar fullerene molecule also can be as the base material of fullerene derivate.
In 1985, in the mass spectrum of the carbon bunch bundle that the laser ablation by graphite produces, found fullerene molecule (H.W.Kroto, J.R.Heath, S.C.O ' Brien, R.F.Curl andR.E.Smalley, Nature, 318,162 (1985)).
After 5 years, promptly set up the method for producing fullerene molecule by the arc discharge of carbon electrode in nineteen ninety.Since having set up practical production method, fullerene molecule has become the focus-of-attention of carbon back semi-conducting material etc.
The present invention has investigated the proton conductive of these fullerene molecule derivatives uniquely and advantageously, the polyhydroxylated fullerene that oh group obtains is introduced in discovery in some carbon atoms of one or more fullerene molecules, even under drying regime, in the wide temperature range that comprises the normal temperature scope (promptly from less than the freezing point of water in greater than the temperature range of the boiling point of water (at least-40 to 160 ℃)), show high proton conductivity, also find introducing the hydrosulphuric acid ester groups to-individual or a plurality of fullerene molecules, promptly-OSO 3When the H group replaced hydroxyl, proton conductive was higher.
More accurately, to rein in alcohol (fullerenol) be to have wherein many hydroxyls to be added to the common name of the fullerene based compound of structure shown in Figure 1A and 1B on one or more fullerene molecules for polyhydroxylated fullerene or richness.Certainly, about the quantity of the hydroxyl of fullerene molecule, arrangement etc., can consider some variations.People such as Chiang have reported first synthetic embodiment (L.Y.Chiang, J.W.Swirczewski, the C.S.Hsu of polyhydroxylated fullerene in 1992, S.K.Chowdhury, S.Cameron and K.Creengan, J.Chem.Soc.Chem.Commun., 1791 (1992)).From this report, contain the specified quantitative or the polyhydroxylated fullerene of polyhydroxy group more, become the focus of attention at it aspect water-soluble, and mainly studied at biological technical field.
In one embodiment, latest find of the present invention, fullerene derivate can form from the aggregation of polyhydroxylated fullerene molecule, schematically illustrate as Fig. 2 A, wherein, the hydroxyl (in the drawings, O represents polyhydroxylated fullerene molecule) of each molecule of these contiguous molecules interacts mutually, thereby in the integral body of polyhydroxylated fullerene molecule or aggregation, show high proton conductivity (that is H between the phenolic hydroxyl group at one or more polyhydroxylated fullerene molecules, +The high rate of transform).
As proton conductor in this embodiment, can use wherein each perhaps polymolecular have in a large number-OSO 3The aggregation of the fullerene molecule of H group replaces the aggregation of polyhydroxylated fullerene molecule previously discussed.People such as Chiang have reported wherein usefulness-OSO shown in Fig. 2 B in 1994 3The H group replaces the fullerene based compound of OH group, i.e. the richness of hydrosulphuric acid esterification is reined in pure F (polyhydroxy hydrosulphuric acid esterification fullerene) (L.Y.Chiang, L.Y.Wang, J.W.Swirczewski, S.Soled and S.Cameron, J.Org.Chem.59,3960 (1994)).Polyhydroxy hydrosulphuric acid esterification fullerene can only contain-OSO 3H group or contain-OSO 3H group and some hydroxyls.
The preparation fullerene derivate of the present invention situation under, prepared contain hydroxyl or-OSO 3The aggregation of a large amount of fullerene derivate molecules of H group or its mixture.Since come from the great amount of hydroxy group that contained originally in the described molecule or-OSO 3The proton Direct Transfer of H group or its mixture, so, the integral body of these fullerene molecules or the proton conductive of aggregation are that the oneself determines, do not need to entrain into from the hydrogen of stream molecule or from the proton in the atmosphere, do not need from external environment condition, to provide water yet, particularly do not need adsorbed water etc. from atmosphere.In other words, the proton conductive of aggregation that contains the fullerene derivate molecule of functional group is not subjected to the restriction of ambiance.
In addition, have the electrophilic performance especially as the fullerene molecule of fullerene derivate base material, this performance not only can so that have peracidity-OSO 3The H group, and can be so that hydroxyl promotes the ionization of hydrogen to a great extent.This is one of the proton conductor of a kind of embodiment of the present invention reason of showing excellent proton conductive.
According to the proton conductor of a kind of embodiment of the present invention and since can to the fullerene molecule of each or a plurality of fullerene derivates introduce great amount of hydroxy group or-OSO 3H group or its mixture, the proton number metric density relevant with unit volume conductor conductivity becomes very high.This is the Another reason that proton conductor in this embodiment shows effective conductivity.
Because the main carbon atoms of fullerene molecule of the fullerene derivate of the proton conductor in the present embodiment or form by carbon atom substantially, therefore, fullerene derivate in light weight, be not easy to decompose, purer, promptly do not contain the pollutant that adverse effect can be arranged the proton conductive performance of its hope relatively.In addition, produce the cost reduction rapidly that fullerene derivate needs.Therefore, the aspect of other hope of discussing according to resource, environment, economy or front can think that fullerene derivate is desirable carbonaceous material.
Because the present invention, further found proton dissociation group as discussed above be not limited to hydroxyl or-OSO 3H functional group.
More clearly, the proton dissociation group can represent that, X is arbitrary atom or the atomic group with divalence with chemical molecular formula-XH here, in addition this group can with chemical molecular formula-OH or-YOH represents that, Y is arbitrary atom or the atomic group with divalence here.
Especially, the proton dissociation group preferably-OH and-OSO 3H and-COOH ,-SO 3H and-OPO (OH) 3Functional group at least a.
According to the present embodiment, electron attractive group, as nitro, carbonyl and carboxyl, itrile group, haloalkyl or halogen atom (fluorine or chlorine atom) preferably can be incorporated into the carbon atom of one or more fullerene molecules with the proton dissociation group.Fig. 2 C represents that also to the fullerene molecule of wherein introducing Z, wherein, Z represents-NO except the-OH 2,-CN ,-F ,-Cl ,-COOR ,-CHO ,-COR ,-CF 3Or-SO 3CF 3(R is an alkyl) electron attractive group at least a.Because except functional group, also there is electron attractive group, from the proton dissociation group between functional group so proton discharges easily and the electronics sucking action by electron attractive group transmits.
According to the present embodiment, the quantity of proton dissociation group can freely be selected in the carbon atom number range less than fullerene molecule, preferably comprises 5 functional groups or more.In order to keep the pi-electron characteristic of fullerene molecule so that obtain effective electronics attraction power, the quantity of functional group more preferably fullerene molecule carbon number half or less than its half.
For the synthetic above-mentioned fullerene derivate that is used for a kind of proton conductor of embodiment, as the back that reference example is described, the powder that can make fullerene molecule is through known processing, as the acid treatment and the hydrolysis of appropriate combination, introduce the proton dissociation group of wishing to the carbon atom of each or some fullerene molecule of fullerene derivate.
After processing, the powder of the fullerene derivate that is obtained can be pressed into desirable shape, and for example compacting in flakes.The compacting of powder can not use any adhesive to carry out, and this strengthens proton conductive effectively, and reduces the weight of proton conductor, produces the moulding material that mainly contains fullerene derivate.
Proton conductor in the present embodiment can be used for various electrochemical appliances suitably.For example, the present invention can be preferably used for a kind of electrochemical appliance, and its basic structure comprises first kind and second kind of electrode and the proton conductor between the two, and wherein, described proton conductor is the proton conductor in the present embodiment.
More specifically, proton conductor in the present embodiment can be preferably used for wherein that at least a of first kind and second kind electrode is a kind of electrochemical appliance of gas electrode, and perhaps wherein at least a of first kind and second kind electrode is the electrochemical appliance of active electrode.
Hereinafter, will an embodiment who the proton conductor of the present embodiment is applied to fuel cell be described.
Fig. 8 represents that proton conductive part 1 wherein remains on the figure that the proton electricity of the fuel cell between first kind of electrode (for example hydrogen electrode) 2 and the second kind of electrode (for example oxygen electrode) 3 is led, wherein, the proton of disassociation or transmission is moved to second kind of electrode 3 one side along the direction shown in the arrow of Fig. 8 from first kind of electrode 2 one side in proton conductive part l.
Fig. 9 is an embodiment of the fuel cell of the expression proton conductor that uses the present embodiment.Construct this fuel cell, make on it or the wherein closely overlapping or negative pole (fuel electrode or hydrogen electrode) 2 that is dispersed with catalyst 2a and leaded 8 towards it on or wherein tight overlapping or be dispersed with the positive pole (oxygen electrode) 3 of catalyst 3a and leaded 9, proton conductive part 1 remains between the two.When using this fuel cell, hydrogen provides from the import 12 of negative pole 2 one sides, discharges from the outlet 13 (not providing sometimes) of negative pole 2 one sides.At fuel (H 2) 14 by in the process of flow channel 15, produce proton.These protons are moved to anodal 3 one sides with the proton that produces in proton conductive part l, oxygen (air) 19 reactions with provide and flow to outlet 18 flow channel 17 from import 16 produce the electromotive force of wishing.
According to the fuel cell with said structure, because the proton that produces in proton conductive part 1 is moved to anodal 3 one sides with the proton that provides from negative pole 2 one sides, it is higher that proton conductive becomes.Therefore, can get rid of needs, therefore simplify the structure of system and reduced the weight of system for any humidifier or other water source or other outside migration medium.
The various details another embodiment.Another embodiment is different from the present embodiment part and is that above-mentioned fullerene derivate mixes use with polymeric material.Yet the proton conductor of second kind of embodiment has the proton conductive feature identical with the present embodiment substantially.
The second kind of proton conductor in the present embodiment contains above-mentioned fullerene derivate (introducing the proton dissociation group in the carbon atom that constitutes fullerene) and polymeric material.
Polymeric material can be one or both or the multiple known polymer with film forming ability.The content of polymeric material is generally 50 weight % or still less.If this content is greater than 50 weight %, the proton conductive of fullerene derivate may reduce.
Because the second kind of proton conductor in this embodiment contains fullerene derivate, it can show the proton conductive that can compare favourably with the proton conductor of the present embodiment.
Though use the proton conductor in the present embodiment that only contains fullerene derivate with aforesaid pressed powder, having can be as the flexible proton conductive film with high strength and airtight performance from the second kind of proton conductor in the present embodiment of the film forming ability of polymeric material.In general, the thickness of proton conductive film is 300 microns or littler.
The kind of polymeric material is restriction especially not, as long as it does not disturb the proton conductive reaction of fullerene derivate etc. (because with) as far as possible and has film shaped performance, but generally can be selected from the polymer that does not have electron conduction and show good stability.The example of these polymer can comprise polyvinyl fluoride, polyvinylidene fluoride and polyvinyl alcohol.The reason that polyvinyl fluoride, polyvinylidene fluoride and polyvinyl alcohol are applicable to the second kind of proton conductor in the present embodiment will be described below.
Polyvinyl fluoride is applicable to that the reason of the second kind of proton conductor is that it has the good film crystallized ability.Even join the amount of the amount of the polyvinyl fluoride in the fullerene derivate, also can easily form film with high-intensity second kind of proton conductor less than other polymeric material.The content of polyvinyl fluoride is 3 weight % or still less, preferably in 0.5-1.5 weight % scope.By add the polyvinyl fluoride in the above-mentioned scope in fullerene derivate, the film of the second kind of proton conductor has the thickness in l micron-100 micrometer range.
Polyvinylidene fluoride or polyvinyl alcohol are applicable to that the reason of the second kind of proton conductor is that it can form effectively and has the proton conductive film that well prevents the gas permeation ability.The content of these materials is preferably in 5-15 weight % scope in this case.
If less than the lower limit of above-mentioned scope, may forming film, the content of polyvinylidene fluoride or vinyl alcohol has a negative impact.
The film of the second kind of proton conductor in the present embodiment can use known film formation technology, waits as extrusion molding, filtration, coating to obtain.
The second kind of proton conductor in the present embodiment preferably can be applied to wherein use in the electrochemical appliance of the proton conductor in the present embodiment.
That is to say that in using the electrochemical appliance of the present embodiment, wherein, proton conductor remains between first kind and the second kind of electrode, proton conductor can replace with the second kind of proton conductor in the present embodiment.
Figure 10 is the schematic diagram that the hydrogen-air cell of the second kind of proton conductor in the present embodiment is used in expression.In this device, hydrogen electrode is towards air electrode 22, the proton conductor 20 (being configured to the second kind of proton conductor) that is molded into film remains between the two, these electrodes 21 and 22 outside remain between the teflon plate 24a and teflon plate 24b in some holes 25, and fixed thereon with bolt 26a and 26b and nut 27a and 27b, the hydrogen electrode lead wire 28a and the air electrode lead wire 28b that stretch out from electrode 21 and 22 are drawn out to the battery outside.
Figure 11 is the schematic diagram that a kind of electrochemical appliance of the second kind of proton conductor in the present embodiment is used in expression.With reference to Figure 11, proton conductor 34 (being configured to the second kind of proton conductor) remains on negative pole 31 that anode active material layer 30 is arranged on its inner surface and its outer surface to be had between the positive pole (gas electrode) 33 of ventilative supporter 32.Negative active core-shell material can be configured to hydrogen adsorbing alloy or by the hydrogen adsorbing alloy that supports as material with carbon elements such as fullerenes.Ventilative supporter 32 may be constructed to the porous carbon paper.Anodal 33 preferably can form by the slurry of coating carbon dust carrying platinum.Space between the outer end of the outer end of negative pole 31 and anodal 33 is blocked with packing ring.In this electrochemical appliance, exist water to charge by making anodal 33 1 sides.
Figure 12 is the schematic diagram of electrochemical appliance of representing wherein to use the second kind of proton conductor of the present embodiment.With reference to Figure 12, the proton conductor 41 that forms film (having the second kind of proton form of conductors) remains on negative pole 38 that anode active material layer 37 is arranged on its inside face and its inner surface to be had between the positive pole 40 of anode active material layer 39.Positive electrode active materials is generally configured to the material that mainly comprises nickel hydroxide.Even in this electrochemical appliance, the space between the outer end of the outer end of negative pole 38 and anodal 40 is blocked with packing ring 42.
Based on the identical mechanism of electrochemical appliance of the proton conductor that uses the present embodiment, use each of above-mentioned electrochemical appliance of the second kind of proton conductor in this embodiment can show good proton conductive effect.In addition, mix the fullerene derivate that uses because the second kind of proton conductor contains with the polymeric material with film forming ability, it can be molded into the high and little film of gas-premeable of intensity, so it can show good proton conductive.
The third embodiment of various details, the third embodiment is different from first kind and second kind of embodiment, because its proton conductor mainly comprises one or more carbon cluster derivative things, but others are identical or similar with second kind of embodiment with first kind, for example the basic function of proton conductive mechanism.
The third proton conductor in the present embodiment mainly comprises the carbon cluster derivative thing, wherein, introduces proton dissociation groups to some carbon atoms as each carbon of carbon cluster derivative thing base material bunch.
What the inventor carried out studies show that, in order to give carbonaceous material gratifying proton conductive, need provide proton conductive approach as much as possible (conductive site or passage) to carbonaceous material.Have been found that if use the as far as possible little carbon of size bunch and introduce two or more protons disassociation substituents, can obtain gratifying proton conductive on the whole in its outside.In this case, aspect acidity, improved the proton conductor of solid shape significantly.Yet, to completely contradict with other carbonaceous material, carbon bunch can not be degenerated and excellent in te pins of durability when oxidation, the composed atom of carbon bunch is combined closely mutually, and the result is that interatomic bond can not rupture, even the acidity height, also be not easy to take place chemical change, therefore can keep membrane structure.
Have in the present embodiment of above-mentioned configuration the third proton conductor in addition under drying regime, also can show with first kind and second kind of embodiment in first kind and each similar high proton conductivity of the second kind of proton conductor.
As defined above, bunch group refers to the aggregation of maximum hundreds of carbon atoms that tightening key lumps together.Because this aggregated structure, improved proton conductive, keep that chemical property provides enough film strengths simultaneously and form laminated construction easily.On the other hand, mainly bunch group that is made up of carbon refers to the aggregation of maximum hundreds of carbon atoms that tightening key lumps together, and the carbon-to-carbon molecule-type key that exists between the carbon atom has nothing to do.Should be noted that carbon bunch, the aggregation that promptly mainly contains carbon atom needn't be made up of carbon atom fully.In this respect, its major part is that the atom set of carbon atom is defined as carbon bunch in this article.The aggregation of in Fig. 4-7, having represented various carbon bunch or carbon atom.In these figure, do not represent the proton dissociation group, for example hydroxyl.Find out that from these figure the material that is used for proton conductor can have wide range of choice.
Fig. 4 represents to have the carbon bunch of spherical structure similar with it, elliposoidal structure and planar structure.Fig. 5 represents to have the carbon bunch of the spherical structure that part opens wide, and has been characterised in that one or more open ends.Producing by arc discharge in the fullerene molecule process,, produce the carbon bunch of the spherical structure that has the band open end in a large number as byproduct.Fig. 6 represents each carbon that has diamond lattic structure bunch, and wherein most of carbon atom of carbon bunch is in SP 3The bonding state.
Wherein most of carbon atom is in SP 2The carbon clustered materials of bonding state, if it has the planar structure of graphite, perhaps all or part of is fullerene or nano tube structure, then the base material as proton conductor is undesirable, because it is usually because SP 2Bonding and have electron conduction.
On the contrary, has SP 2The fullerene or the nano tube structure of bonding do not have electron conduction, because it also partly contains the SP that shows hope 3The element of bonding is so it is desirable as the proton conductor base material.
Fig. 7 represents the carbon that mutually combines bunch.Therefore, Fig. 7 represents to be used for to be manufactured on the example of carbon bunch of carbon cluster derivative thing of proton conductor of a kind of embodiment of the third proton conductor of the present invention.
In order to form the third proton conductor in the present embodiment, require in bunch group or carbon bunch, to introduce the proton dissociation group.In addition, further introducing electron attractive group in each of bunch group or carbon bunch may wish.According to following production method, the proton dissociation group can be incorporated in each carbon bunch.
In accordance with the present production process, produce the carbon formed by carbon dust bunch by the lonely discharge of the electricity of carbon-based electrode, and suitably make carbon bunch through peracid treatment, be typically and use sulfuric acid and hydrolysis, and also through oversulfonate or phosphineization, so that introduce sulfenyl functional group or phosphorus base functional group respectively, can easily obtain the carbon cluster derivative thing.
The carbon cluster derivative thing can be pressed into suitable shape, for example disk.According to the third proton conductor in the present embodiment, each main axis length as the carbon of the carbon cluster derivative thing base material of proton conductor bunch can be 100 nanometers or littler, 10 nanometers or littler preferably, wherein the number of functional groups of Yin Ruing is preferably 2 or more.
The carbon that is used for the third proton conductor bunch can have the cage structure that its part at least has open end.Carbon with this defect sturcture bunch has reactivity like the fullerene, and at its defect part (being its open end part) higher activity is arranged.Therefore, use each bunch base material of the carbon with this defect sturcture (being open end) can promote by introducing proton disassociation substituents such as acid treatments as the third proton conductor, promptly increase the introducing efficient of proton disassociation substituent, thereby increase the proton conductive of the third proton conductor.In addition, compare, can synthesize a large amount of carbon bunch, therefore can produce carbon bunch with low-down cost with fullerene molecule.
Being incorporated into can be with above-mentioned identical as the kind of the functional group of each carbon of the third proton conductor base material in the present embodiment bunch and electron attractive group.
The third proton conductor in the present embodiment can suitably be applied in the various electrochemical appliances, for example fuel cell.In this case, the structure of electrochemical appliance can be substantially with use first kind or second kind of embodiment in first kind or the electrochemical appliance of the second kind of proton conductor identical, still, first kind or the second kind of proton conductor are with the third proton conductor replacement.Because the third proton conductor in the present embodiment even under drying regime, also can show good proton conductive, so, needs to providing any humidifier or other to produce the similar device of outside migration (as water or steam) can be provided, therefore can simplied system structure and reduce system weight.
The 4th kind of embodiment of various details, wherein, proton conductor comprises a kind of tubulose carbonaceous material derivative.
Tubulose carbonaceous material derivative comprises a kind of tubulose carbonaceous material as its base material.The tubulose carbonaceous material comprises a kind of CNT material, and by the nanotube molecular composition, each nanotube molecular diameter is about several nanometers or littler, is typically in the 1-2 nanometer range.Except the CNT material, the tubulose carbonaceous material comprises a kind of CNF material, and by the nanofiber molecular composition, each nanofiber molecular diameter is several nanometers or bigger, and maximum can reach 1 millimeter.In addition, known CNT material comprises by the molecular Single Walled Carbon Nanotube of nanotube (SWCNT) material, each nanotube molecule is formed by individual layer, and perhaps by the molecular multi-walled carbon nano-tubes of nanotube (MWCNT), each nanotube molecule is made up of concentric overlapping two-layer or multilayer.SWCNT and MWCNT molecule are illustrated respectively among Figure 13 A and the 13B.In addition, the description of CNT, SWCNT and MWCNT only is illustrative, wherein should be appreciated that to the invention is not restricted to this.
According to the 4th kind of embodiment of the present invention, the proton dissociation group that is incorporated in the tubulose carbonaceous material in order to form tubulose carbonaceous material derivative comprises the identical proton dissociation group of discussing about other embodiment of the present invention with the front.Just as described, Figure 14 represents to contain a kind of example of the tubulose carbonaceous material derivative of hydroxy functional group.In addition, Figure 15 shows a plurality of tubulose carbon-containing molecules or the tracheary element of tubulose carbonaceous material derivative as shown in figure 14.Equally, Figure 16 represents to comprise-OSO 3The tracheary element of the another kind of tubulose carbonaceous material derivative of H functional group.
For to tubulose carbonaceous material introducing-OSO 3H functional group, to form its derivative, by the tubulose carbonaceous material of preparation halogenation, and the material that makes halogenation is produced this tubulose carbonaceous material derivative through using the acid treatment of sulfuric acid or nitric acid.In addition, can use technology for hydrolyzing to introduce oh group replacement-OSO 3H functional group.If the use hydrolysis, in order to replace hydroxyl with different functional group, as-OSO 3H functional group can carry out acid treatment subsequently.If non-halogenated tubulose carbonaceous material is as base material or raw material, so that form tubulose carbonaceous material derivative, so, this material can be through using the acid treatment of sulfuric acid or nitric acid, as previously discussed.Tubulose carbonaceous material about halogenation preferably uses fluorine.
Not only can be by above-mentioned wet method, and can produce tubulose carbonaceous material derivative by the dry method of following use plasma.In this method, non-halogenated tubulose carbonaceous material is through the plasma treatment in oxygen, then in order to introduce proton dissociation group (being typically hydroxyl) in the tracheary element of tubulose carbonaceous material, through the plasma treatment under hydrogen.
Above-mentioned only is the explanation of the preferred manufacture method of tubular carbonaceous material, the invention is not restricted to this.
The present invention has studied the proton conductive of these tubulose carbonaceous material derivatives, find that these materials are in comprising all temps scope in normal temperature zone, promptly, provide high proton conductivity from the freezing point that is lower than water in the temperature range of the boiling point that is higher than water (at least-40 ℃-160 ℃).The present invention finds that also proton conductive is higher for comprising the tubulose carbonaceous material derivative of hydrosulphuric acid ester as its group replacement oh group.
Especially, polyhydroxylated SWCNT material is to have the common name that many hydroxyls is added to the derivative of the structure on some tracheary elements in order to form SWCNT material shown in Figure 14.Certainly, about the quantity of oh group, arrangement etc., can consider some variations within the scope of the invention.Latest find of the present invention, the aggregation of the polyhydroxylated tracheary element shown in Figure 14 and 15, it is polyhydroxylated SWCNT material, wherein the oh group of contiguous tracheary element interacts mutually, show high proton conductivity, i.e. the H of contained phenolic hydroxyl group group in each tracheary element from polyhydroxylated SWCNT material or integral material +Or the transmission of hydrogen proton or transfer ability height.
By main-OSO a plurality of by having 3The tubular carbonaceous material derivative aggregation of H group is (if any a plurality of-OSO 3The aggregation of the SWCNT of H group) proton conductor of Zu Chenging has also reached purpose of the present invention.On the other hand, wherein-OSO 3The hydrosulphuric acid ester SWCNT of H group replacement-OH group can only contain-O5O 3The H group as shown in figure 16, perhaps can contain a plurality of oh groups and a plurality of-OSO simultaneously in a molecule 3The H group.
The same with the proton conductive of other proton conductor embodiment, the proton conductive that comprises the tubulose carbonaceous material derivative of the tracheary element aggregation with a plurality of functional groups is not subjected to the restriction of environmental condition.Like this, in order to realize ideal effect of the present invention, be unnecessary from the additional proton source (as water) of moving medium.
Similar with other embodiment, the reason that tubulose carbonaceous material derivative can show this desirable proton conductive effect is that a large amount of functional groups can be incorporated on some tracheary elements of tubulose carbonaceous material, makes that the proton density corresponding with unit volume conductor conductivity is very big.
This outer tubular carbonaceous material derivative mainly is made up of the carbon atom of each tracheary element, thus in light weight, and be not easy to decompose, do not contain any pollutant yet.In addition, the tubulose carbonaceous material that is used to produce its derivative base material can come low-cost production by the catalysis thermal decomposition of hydrocarbon.Therefore, because resource, environment and economic aspect, the tubulose carbonaceous material is considered to desirable material (Carbon Vol.36, No.11, pp.1603-1612,1998).
According to the research of the inventor to the proton dissociation group, the proton dissociation group be not limited to hydroxyl or-OSO 3H functional group is as long as they can give preferred proton conductive.
More clearly, the proton dissociation group can represent that, X is arbitrary atom or the atomic group with divalence with chemical formula-XH here, described in addition group can with chemical molecular formula-OH or-YOH represents that, Y is arbitrary atom or the atomic group with divalence here.
Especially, the proton dissociation group preferably-OH and-OSO 3H and-CDOH ,-SO 3H and-OPO (OH) 3Functional group at least a.
Equally, the proton dissociation group that is incorporated in these derivatives is arranged in mode same with the above-mentioned embodiment.
According to the present embodiment, electron attractive group, as nitro, carbonyl and carboxyl, itrile group, haloalkyl or halogen atom (fluorine or chlorine atom) preferably can be incorporated on the carbon atom of tubulose carbonaceous material with the proton dissociation group.For example, can introduce to SWCNT-NO 2,-CN ,-F ,-Cl ,-COOR ,-CHO ,-COR ,-CF 3Or-SO 3CF 3(R is an alkyl) electron attractive group, and proton dissociation group are as the OH group.Because except functional group, also there is electron attractive group, from the proton dissociation group between functional group so proton discharges easily and the electronics sucking action by electron attractive group transmits.
About the proton dissociation group quantity of tubulose carbonaceous material derivative, this quantity is limited to the degree less than the carbon number of tubulose carbonaceous material derivative.In addition, the restricted number of functional group is in the degree that must eliminate electron conduction.For example, for the SWCNT material, preferably per 10 carbon atoms of this quantity are one or more.
The proton conductor of the present embodiment mainly is made up of above-mentioned tubular carbonaceous material, and can contain other composition that does not hinder or improve proton conductive.In these other compositions, most preferably wherein introduced the fullerene derivate of above-mentioned proton dissociation group.
In the advantage of tubular carbonaceous material, compare with the complexity winding of its axial length and each structure, there is the axial length of tangible pipe, as discussed above.Because these advantages, when being applied to electrochemical appliance, flocking together with the fullerene derivate of spherical molecule and to compare, can form stronger more stable film.Yet, owing under the fullerene situation, can more easily introduce the reaction of proton dissociation group, therefore, can produce higher conductivity, so, feel that it is better optionally using these two kinds of materials according to special-purpose.
If in order to produce the composite material of forming by two kinds of different materials, mix and use the fullerene derivate of wherein having introduced the tubular carbonaceous material of proton dissociation group and wherein having introduced the proton dissociation group, can obtain further excellent function.
According to the present invention, tubulose carbonaceous material derivative can be formed for the film of electrochemical appliances such as fuel cell ideally.
These materials can pass through known extrusion technology, more preferably are dispersed in tubulose carbonaceous material derivative in the liquid and filter this dispersion to be molded into film.Generally make the water equal solvent as liquid.Yet liquid is not specially limited, as long as derivative can be dispersed in the liquid.
By filtering dispersion, tubulose carbonaceous material derivative is deposited on the filter with film shape.This film does not contain any adhesive and only is made up of tubulose carbonaceous material derivative, and wherein, tracheary element twines with the form of complexity.This film has very high intensity, can easily peel off from filter.
In this case, be dispersed in the liquid, may easily form the laminated film of forming by these mixtures of material, still do not contain any adhesive if fullerene derivate mixes with tubulose carbonaceous material derivative.
The proton conductor of this embodiment preferably is used for fuel cell.With the same in the embodiment of front, the structure of fuel cell as shown in Figure 9.
Hereinafter will describe the present invention in detail based on embodiment.
Synthesizing of the polyhydroxylated fullerene of＜embodiment 1 〉
With reference to L.Y.Chaing, L.Y.Wang, J.W.Swircczewski, S.Soled and S.Cameron, J.Org.Chem.59,3960 (1994), carry out the synthetic of polyhydroxylated fullerene.At first, 2 grams are contained the 15%C that has an appointment 70C 60And C 70Mix powder is placed in 30 milliliters of oleums, stirs 3 days and remains in 600 ℃ the blanket of nitrogen.Reactant is placed in the anhydrous diethyl ether that cools off in the ice bath at leisure, tells sediment, use the diethyl ether washed twice, and be the mixture washed twice of 2: 1 diethyl ether and acetonitrile with mixing ratio by centrifugation, and at 40 ℃ of drying under reduced pressure.Be placed in 60 milliliters of ion exchange waters washing also dry sediment like this, stirred 10 hours, use nitrogen bubble simultaneously at 85 ℃.Reactant passes through centrifugation then, and sediment separate out with pure water the sediment washing for several times, passes through centrifugation repeatedly, and at 40 ℃ of drying under reduced pressure.The brown ceramic powder that is obtained is measured through FI-IR.As a result, the IR of brown ceramic powder spectrum almost with the C shown in the above-mentioned document 60(OH) 12Unanimity, so, confirmed that this powder is the polyhydroxylated fullerene as target product.For example, for C 60, above-mentioned reaction is expressed as follows:
Figure C0081055600201
The production of the polyhydroxylated fullerene aggregation disk of＜embodiment 1 〉
Then, 90 milligrams of polyhydroxylated fullerene powder are pressed in one direction the disk of 15 millimeters of diameters with about 5 tons/square centimeter pressure.Because but the briquettability of polyhydroxylated fullerene powder is good, although do not conform to adhesive resin in the powder, the polyhydroxy fullerene powder still can easily be molded into the about 300 microns disk of thickness.This disk is as the disk of embodiments of the invention 1.
The hydrosulphuric acid ester esterification of＜embodiment 2 gathers the synthetic of hydrogenated fullerene thing (all esterifications) 〉
Carry out the synthetic of hydrosulphuric acid esterification fullerene with reference to above-mentioned document.At first, 1 gram polyhydroxy fullerene powder is placed in 60 milliliters of oleums, stirred 3 days and remained in the blanket of nitrogen of normal temperature.Reactant being placed in the anhydrous diethyl ether that cools off in the ice bath at leisure, telling sediment by centrifugation, with diethyl ether washing three times, and is the mixture washed twice of 2: 1 diethyl ether and acetonitrile with mixing ratio, and at 40 ℃ of drying under reduced pressure.The powder that is obtained is measured through FI-IR.As a result, the IR of powder spectrum almost with the wherein oh group shown in the above-mentioned document fully by the hydrosulphuric acid ester group, promptly-OSO 3The hydrosulphuric acid esterification fullerene unanimity that the H group replaces, so, confirmed that this powder is the hydrosulphuric acid esterification fullerene as target product.
For example, for C 60(OH) y, above-mentioned reaction is expressed as follows (here and hereinafter):
The production of the poly-hydrogenated fullerene thing aggregation disk of the hydrosulphuric acid esterification of＜embodiment 2 〉
Then, 70 milligrams of hydrosulphuric acid esterification fullerene powder are pressed in one direction the circular disk of 15 millimeters of diameters with about 5 tons/square centimeter pressure.Because but the briquettability of hydrosulphuric acid esterification fullerene powder is good, although do not give up adhesive resin in the powder, hydrosulphuric acid esterification fullerene powder still can easily be molded into the about 300 microns disk of thickness.This garden sheet is as of the present invention
The disk of embodiment 2.
Synthesizing of the poly-hydrogenated fullerene thing (partial esterification) of＜part hydrosulphuric acid ester esterification 〉
At first, 2 grams are contained the 15%C that has an appointment 70C 60And C 70Mix powder is placed in 30 milliliters of oleums, and remains in 60 ℃ of nitrogen atmospheres and to stir three days, and reactant is put into the diethyl ether that ice bath cools off at leisure.Should be noted that the diethyl ether of use without dehydration.Telling the sediment of gained by centrifugation, with diethyl ether washing three times, and is the mixture washed twice of 2: 1 diethyl ether and acetonitrile with mixing ratio, and at 40 ℃ of drying under reduced pressure.The powder that is obtained is measured through FI-IR.As a result, the IR of powder spectrum almost contains hydroxyl and OSO with time shown in the above-mentioned document 3The fullerene derivate unanimity of H group, so, confirmed that this powder is the polyhydroxy hydrosulphuric acid esterification fullerene as target product.For example, for C 60, above-mentioned reaction is expressed as follows (here and hereinafter):
Figure C0081055600221
The production of the poly-hydrogenated fullerene thing aggregation disk of the hydrosulphuric acid ester esterification of＜embodiment 3 〉
Then, 80 milligrams of polyhydroxylated hydrosulphuric acid esterification fullerene powder are pressed in one direction the circular disk of 15 millimeters of diameters with about 5 tons/square centimeter pressure.Because but the briquettability of polyhydroxy hydrosulphuric acid esterification fullerene powder is good, although do not contain adhesive resin in the powder, polyhydroxy hydrosulphuric acid esterification fullerene powder still can easily be molded into the about 300 microns disk of thickness.This disk is as the disk of embodiments of the invention 3.
The production of＜comparative example 1 fullerene aggregation disk 〉
In order to contrast, 90 milligrams of fullerene molecule powder as the raw material of synthetic usefulness in the foregoing description are pressed in one direction the disk of 16 millimeters of diameters with about 5 tons/square centimeter pressure.Because but the briquettability of fullerene molecule powder is good, although do not contain adhesive resin in the powder, the fullerene molecule powder still can easily be molded into the about 300 microns disk of thickness.This disk is as comparative example's 1 of the present invention disk.
The proton conductive of embodiments of the invention 1-3 and comparative example's 1 disk is measured
Each proton conductive for the disk of measuring embodiments of the invention 1-3 and comparative example 1, the two sides of this disk remains between the aluminium sheet, the diameter of each aluminium sheet is identical with the disk diameter, promptly 15 millimeters, apply the alternating voltage that frequency range is 7MHz-0.01Hz (amplitude: 0.1 volt) to the garden sheet, measure the complex impedance under each frequency.Measurement is carried out in dry air.
About above-mentioned impedance measurement, proton conductive part 1 equivalent electric circuit shown in the pie graph 17A on electricity of the proton conductor of forming by above-mentioned disk, wherein, electric capacity 6 and 6 ' forms between first kind and second kind of electrode 2 and 3, and the proton conductive part of representing with the parallel circuits of resistance 4 and electric capacity 51 remains between two electrodes.In addition, the hysteresis effect (phase lag under the high frequency) during electric capacity 5 expression protolysis, the difficult parameters of resistance 4 expression protolysis.
Measured impedance Z is represented with formula Z=Re (Z)+iIm (Z).Studied the frequency dependence of the proton conductive part of representing by above-mentioned equivalent electric circuit.
In addition, Figure 17 B represents to use the equivalent electric circuit of the proton conductor (above-mentioned comparative example 1) of the typical fullerene molecule that does not have functional group.
Figure 18 represents the measurement result of impedance of embodiments of the invention 1 and comparative example's 1 disk.
With reference to Figure 18, for comparative example 1, the frequency characteristic of complex impedance is almost identical with the behavior of single capacitor, does not observe the electricity of the charged particle (electronics, ion etc.) of fullerene molecule aggregation at all and leads; And for embodiments of the invention 1, but the impedance meter of high-frequency region reveals the very smooth single semi arch that flattens, the electricity that shows some charged particle in the disk is led, the imaginary part of impedance raises rapidly at low frequency region, show along with moving closer to direct voltage, the obstruction of the charged particle between aluminium electrode and the disk takes place.About the obstruction of aluminium electrode in inventive embodiments 1 and the charged particle between the disk, the charged particle of aluminium electrode one side is an electronics, therefore, be apparent that the charged particle in disk is not electronics or hole, but ion more clearly, is because the proton that the fullerene derivate structure produces.
The conductivity of above-mentioned charged particle can be calculated based on the intercept of high frequency side circular arc and X-axis.For the disk of embodiments of the invention 1, the conductivity of charged particle becomes about 5 * 10 -6S/cm.Embodiments of the invention 2 and 3 disk are through identical as mentioned above measurement.As a result, in each of embodiments of the invention 2 and 3, the global shape of each impedance frequency characteristic and embodiments of the invention 1 are similar; Yet, as shown in table 1, be different in charged particle conductivity in each of the embodiments of the invention 2 that obtain of basis and 3 and the embodiments of the invention 1 in the circular arc portion and the intercept of X-axis.
Table 1: the conductivity of the proton conductor disk of embodiments of the invention 1,2 and 3 (25 ℃)
The disk kind Conductivity (S/cm)
Embodiments of the invention 1 5×10 -6
Embodiments of the invention 2 9×10 -4
Embodiments of the invention 3 2×10 -5
As shown in table 1, contain-OSO 3The conductivity of the fullerene derivate disk of H group causes the ionization of hydrogen easier than hydroxyl.The result of table 1 also show contain hydroxyl and-OSO 3The fullerene derivate aggregation of H group can show good proton conductive at normal temperatures in dry gas.
Secondly, in 160 ℃ to-40 ℃ temperature range, measure the complex impedance of the disk of producing in the embodiments of the invention 1, based on the circular arc portion of the high frequency side of the complex impedance curve of the disk measured under each temperature, calculate the conductivity of disk, investigate the temperature dependency of conductivity.Result as shown in figure 19 (Arrhenius curve) is apparent that conductivity linearly changes or changes with linear mode about the variations in temperature in 160 ℃ to-40 ℃ measurement temperature range.In other words, the data of Figure 19 show that the single ionic electrical conduction mechanism occurs in 160 ℃ to-40 ℃ temperature ranges at least.So the proton conductor that mainly comprises fullerene derivate according to the present invention can show good proton conductive at-40 ℃ that comprise normal temperature to 160 ℃ wide temperature range.
Form the film that comprises polyhydroxy fullerene of embodiment 1 and the generator experimental of this film of use
The polyhydroxylated fullerene powder 0.5 of embodiment among the embodiment 1-3 1 gram and 1 is restrained oxolane (THF) mix,, polyhydroxy fullerene is dissolved among the THF fully mixture ultrasonic vibration 10 minutes.Behind the preparation carbon electrode, form the polyhydroxy fullerene film through the following steps: the plastics mask coated electrode surface with having rectangular aperture, in opening, splash into above-mentioned solution, this solution distributes in opening, it is at room temperature dry so that evaporation THF removes mask.There is its lower surface of equivalent the above-mentioned electrode of catalyst to be placed on the film.Top electrode is finished compound with about 5 tons/square centimeter pressure compacting.This composite material is incorporated in as shown in Figure 9 the fuel cell.Provide hydrogen by a electrode, provide air, carry out generator experimental to another electrode to fuel cell.
Experimental result is shown among Figure 20.With respect to the current value of this fuel cell, about 1.2 volts of open circuit voltage, the characteristic of closed circuit voltage also is good.
The production of the polyhydroxy fullerene 4A disk of＜embodiment 4 〉
At first, 70 milligrams in fullerene derivate powder and 10 milligrams of polyvinylidene fluoride powder by above-mentioned synthetic acquisition, then, to wherein adding 0.5 milliliter of dimethyl formamide, the powder that is mixed stirs in solvent.The circular die of 15 millimeters of this mixture injection diameters, solvent evaporated under reduced pressure.Then, the mixture behind evaporating solvent wherein is pressed into the disk of 15 millimeters of diameters, 300 microns of thickness.This disk is as the disk 4A of embodiments of the invention 4.
The production of the polyhydroxy fullerene 4B disk of＜embodiment 4 〉
Similarly, 70 milligrams of fullerene derivate powder are mixed with the dispersion that contains 60% polytetrafluoroethylene (PTFE) fine powder, its hybrid mode makes PTFE content become 1 weight % (based on total amount), and mixes.The mixture forming that is mixed is become the disk of 15 millimeters of diameters, 300 microns of thickness.This disk is as the disk 4B of embodiments of the invention 4.
Synthesizing of the hydrosulphuric acid ester esterification hydrogenated fullerene thing of＜embodiment 5 (all esterifications) 〉
Carry out the synthetic of hydrosulphuric acid esterification fullerene with reference to above-mentioned document.At first, 1 gram polyhydroxy fullerene powder is placed in 60 milliliters of oleums, stirred 3 days and remained in the blanket of nitrogen of normal temperature.Reactant being placed in the anhydrous diethyl ether that cools off in the ice bath at leisure, telling sediment by centrifugation, with diethyl ether washing three times, and is the mixture washed twice of 2: 1 diethyl ether and acetonitrile with mixing ratio, and at 40 ℃ of drying under reduced pressure.The powder that is obtained is measured through FI-IR.As a result, the IR of powder spectrum is that the fullerene derivate of hydrosulphuric acid foundation group is consistent with the wherein oh group shown in the above-mentioned document fully almost, so, confirmed that this powder is the hydrosulphuric acid esterification fullerene as target product.
The hydrosulphuric acid ester esterification of＜embodiment 5 gathers the production of the disk 5A of hydrogenated fullerene thing (all esterifications) 〉
At first, 70 milligrams in hydrosulphuric acid esterification fullerene derivate powder and 10 milligrams of polyvinylidene fluoride powder, then, to wherein adding 0.5 milliliter of dimethyl formamide, the powder that is mixed stirs in solvent.The circular die of 15 millimeters of this mixture injection diameters, solvent evaporated under reduced pressure.Then, the mixture behind evaporating solvent wherein is pressed into the disk of 15 millimeters of diameters, 300 microns of thickness.This disk is as the disk 5A of embodiments of the invention 5.
The hydrosulphuric acid ester esterification of＜embodiment 5 gathers the production of the disk 5B of hydrogenated fullerene thing (all esterifications) 〉
Similarly, 70 milligrams of hydrosulphuric acid esterification fullerene powder are mixed with the dispersion that contains 60% polytetrafluoroethylene (PTFE) fine powder, its hybrid mode makes PTFE content become 1 weight % (based on total amount) and mixes.The mixture forming that is mixed is become 15 millimeters of diameters, the about 300 microns disk of thickness.This disk is as the disk 5B of embodiments of the invention 5.
Synthesizing of the poly-hydrogenated fullerene thing (partial esterification) of the hydrosulphuric acid ester esterification of＜embodiment 6 〉
At first, 2 grams are contained the 15%C that has an appointment 70C 60And C 70Mix powder is placed in 30 milliliters of oleums, and remain on 60 ℃=-stirred three days in the nitrogen atmosphere, reactant is put into the diethyl ether that ice bath cools off at leisure.Should be noted that the diethyl ether of use without dehydration.Telling the sediment of gained by centrifugation, with diethyl ether washing three times, and is the mixture washed twice of 2: 1 diethyl ether and acetonitrile with mixing ratio, and at 40 ℃ of drying under reduced pressure.The powder that is obtained is measured through FI-IR.As a result, the IR of powder spectrum almost contains hydroxyl and OSO with time shown in the above-mentioned document 3The fullerene derivate unanimity of H group, so, confirmed that this powder is the polyhydroxy hydrosulphuric acid esterification fullerene as target product.
The production of the disk 6A of the poly-hydrogenated fullerene thing (partial esterification) of the hydrosulphuric acid ester esterification of＜embodiment 6 〉
At first, 70 milligrams in polyhydroxy hydrosulphuric acid esterification fullerene derivate powder and 10 milligrams of polyvinylidene fluoride powder, then, to wherein adding 0.5 milliliter of dimethyl formamide, the powder that is mixed stirs in solvent.The circular die of 15 millimeters of this mixture injection diameters, solvent evaporated under reduced pressure.Then, the mixture behind evaporating solvent wherein is pressed into the disk of 15 millimeters of diameters, 300 microns of thickness.This disk is as the disk 6A of embodiments of the invention 6.
The production of the disk 6B of the poly-hydrogenated fullerene thing (partial esterification) of the hydrosulphuric acid ester esterification of＜embodiment 6 〉
Similarly, 70 milligrams of polyhydroxy hydrosulphuric acid esterification fullerene powder are mixed with the dispersion that contains 60% polytetrafluoroethylene (PTFE) fine powder, its hybrid mode makes PTFE content become 1 weight % (based on total amount) and mixes.The mixture forming that is mixed is become 15 millimeters of diameters, the about 300 microns disk of thickness.This disk is as the disk 6B of embodiments of the invention 6.
The production of＜comparative example 2 fullerene disk 〉
In order to contrast, being used as synthetic 90 milligrams in fullerene molecule powder and 10 milligrams of polyvinylidene fluoride powder with raw material in the foregoing description, then, to wherein adding 0.5 milliliter of dimethyl formamide, the powder that is mixed stirs in solvent.The circular die of 15 millimeters of this mixture injection diameters, solvent evaporated under reduced pressure.Then, the mixture behind evaporating solvent wherein is pressed into the disk of 15 millimeters of diameters, 300 microns of thickness.This disk is the disk of embodiment 2 as a comparison.
The production of＜comparative example 3 fullerene disk 〉
In order to contrast, mixing with the dispersion that contains 60% polytetrafluoroethylene (PTFE) fine powder as 70 milligrams in synthetic fullerene molecule powder with raw material in the foregoing description, its hybrid mode makes PTFE content become 1 weight % (based on total amount) and mixes.The mixture forming that is mixed is become 15 millimeters of diameters, the about 300 microns disk of thickness.This disk is the disk of embodiment 3 as a comparison.
The proton conductive of embodiments of the invention 4-6 and comparative example's 2 disk is measured
For each of the disk of measuring embodiments of the invention 4-6 and comparative example 2 proton conductive, the two sides of disk remains between the aluminium sheet, the diameter of each aluminium sheet is identical with the disk diameter, promptly 15 millimeters, apply the alternating voltage that frequency range is 7MHz-0.01Hz (amplitude: 0.1 volt) to disk, measure the complex impedance under each frequency.Measurement is carried out in dry air.
About above-mentioned impedance measurement, proton conductive part 1 equivalent electric circuit shown in the pie graph 17A on electricity of the proton conductor of forming by above-mentioned disk, wherein, electric capacity 6 and 6 ' forms between first and second electrodes 2 and 3, and the proton conductive part of representing with the parallel circuits of resistance 4 and electric capacity 51 remains between two electrodes.In addition, the hysteresis effect (phase lag under the high frequency) during electric capacity 5 expression protolysis, the difficult parameters of resistance 4 expression protolysis.Measured impedance Z is represented with formula Z=Re (Z)+iIm (Z).Studied the frequency dependence of the proton conductive part of representing by above-mentioned equivalent electric circuit.In addition, Figure 17 B represents to use the equivalent electric circuit of the proton conductor (comparative example that the back will be described) of the typical fullerene molecule that does not contain the ionic dissociation effect.
Figure 21 represents the measurement result of impedance of the disk 1A of embodiments of the invention 4 and comparative example's 1 disk.
With reference to Figure 21, for comparative example 2, the frequency characteristic of complex impedance is almost identical with the behavior of single capacitor, does not observe the electricity of the charged particle (electronics, ion etc.) of fullerene molecule aggregation at all and leads; And for the disk of embodiments of the invention 4, but the impedance meter of high-frequency region reveals the very smooth single semi arch that flattens, the electricity that shows some charged particle in the disk is led, the imaginary part of impedance raises rapidly at low frequency region, show along with moving closer to direct voltage, the obstruction of the charged particle between aluminium electrode and the disk takes place.About the obstruction of the charged particle between aluminium electrode and comparative example's 4 disk 1A, the charged particle of aluminium electrode one side is an electronics, therefore, be apparent that the charged particle in disk is not electronics or hole, but ion more clearly, is because the proton that the fullerene derivate structure produces.
The conductivity of above-mentioned charged particle can be calculated based on the intercept of high frequency side circular arc and X-axis.For the disk of embodiments of the invention 4, the conductivity of charged particle becomes about 1 * 10 -6S/cm.The disk of the disk 1B of embodiments of the invention 4, the disk of embodiments of the invention 5 and embodiments of the invention 6 is through identical as mentioned above measurement.As a result, the global shape of the impedance frequency characteristic in each disk and embodiments of the invention 4 are similar; Yet, as shown in table 2, be that charged particle conductivity in each disk of obtaining of basis is different with the disk in the embodiments of the invention 4 in the circular arc portion and the intercept of X-axis.
The conductivity of the proton conductor disk in table 2 embodiments of the invention (at 25 ℃)
The disk kind Conductivity (S/cm)
The disk 4A of embodiments of the invention 4 1×10 -6
The disk 5A of embodiments of the invention 5 2×10 -4
The disk 6A of embodiments of the invention 6 6×10 -5
The disk 4B of embodiments of the invention 4 3×10 -6
The disk 5B of embodiments of the invention 5 7×10 -4
The disk 6B of embodiments of the invention 6 3×10 -5
As shown in table 2, in the disk kind A and B of embodiments of the invention 4,5 and 6, contain OSO 3The conductivity of the fullerene derivate disk of H group is greater than the conductivity of the fullerene derivate disk that contains hydroxyl group.Its reason is OSO 3The H group is than the easier ionization that causes hydrogen of hydroxyl.The result of table 2 also shows, contains oh group and OSO 3The fullerene derivate aggregation of H group can show the good proton conductivity under the normal temperature in dry gas.
Secondly, in 160 ℃ to-40 ℃ temperature range, measure the complex impedance of the disk 4A of embodiments of the invention 4, based on the circular arc portion of the high frequency side of the complex impedance curve of the disk measured under each temperature, calculate the conductivity of disk, investigate the temperature dependency of conductivity.The result with the Arrhenius curve representation in Figure 22.Can obviously find out from the data shown in Figure 22, conductivity and temperature at least at 160 ℃ to-40 ℃ temperature range internal memory in linear relationship.In other words, the data of Figure 22 show that the single ionic electrical conduction mechanism can occur in 160 ℃ to-40 ℃ temperature ranges.So the second kind of proton conductor that mainly comprises fullerene derivate and polymeric material according to the present invention can show good proton conductive in comprising the wide temperature range of normal temperature, particularly at 160 ℃ high temperature in-40 ℃ low temperature range.
The production of the carbon cluster derivative thing of＜embodiment 7 〉
In the 0.05MPa argon gas, the electric current that applies 200 peaces between two electrodes being made up of carbon-point carries out arc discharge, thereby obtains 1 gram carbon dust.The oleum of this carbon dust with 100 milliliter 60% mixed, in 60 ℃ of nitrogen current, kept 3 days.Use water-bath to heat.Reaction solution is slowly splashed in 500 ml pure waters, from solution, isolate solid matter by centrifugal separation.With anhydrous diethyl ether for several times, 40 ℃ of drying under reduced pressure 5 hours solid matter washing.In 10 milliliters of oxolanes (THF), by removing by filter insoluble component, solvent evaporated under reduced pressure obtains solid matter, wherein, 50 milligrams of solid matters is pressed into the disk of 15 millimeters of diameters under 5 tons/square centimeter pressure the powder dissolution of gained.This disk is as the disk of embodiments of the invention 7.
The proton conductive of the carbon cluster derivative thing disk of embodiment 7 is measured
In dry air, measure the AC impedance of the disk of embodiments of the invention 7 according to aforesaid same procedure.As a result, confirm because the impedance behavior that ionic conductance produces occurs in 10MHz or lower frequency range.Based on the circular curve diameter of impedance behavior, the conductivity of having calculated the disk of embodiments of the invention 7 is 3.0 * 10 -6(S/cm).
The production of the carbon cluster derivative thing of＜embodiment 8 〉
In the 0.05MPa argon gas, the electric current that applies 200 peaces between two electrodes being made up of carbon-point carries out arc discharge, thereby obtains 1 gram carbon dust.This carbon dust is dissolved in the toluene, and by removing by filter insoluble composition, solvent evaporated under reduced pressure regains powder.The powder of gained mixes with 100 milliliter 60% oleum, keeps 3 days in 60 ℃ of nitrogen current.Use water-bath to heat.Reaction solution is slowly splashed in 500 ml pure waters, from solution, isolate solid matter by centrifugal separation.With anhydrous diethyl ether for several times, 40 ℃ of drying under reduced pressure 5 hours solid matter washing.50 milligrams of solid matters are pressed into the disk of embodiments of the invention 8 under 7 tons/square centimeter pressure.
The proton conductive of the disk of＜embodiment 8 is measured 〉
In dry air, measure the AC impedance of the disk of embodiments of the invention 8 according to aforesaid same procedure.As a result, confirm because the impedance behavior that ionic conductance produces occurs in 10MHz or lower frequency range.Based on the circular curve diameter of impedance behavior, the conductivity of having calculated the disk of embodiments of the invention 8 is 3.4 * 10 -4(S/cm).
The main component of the carbon dust that obtains by arc discharge is carbon bunch or the carbon cluster molecule that does not have closing structure, as cage structure, but has the structure that its part at least has open end.In addition, the molecule that similarly has the structure of good electrical electronic conductivity with graphite-structure that contains slightly in the carbon cluster molecule hinders the effect of the ion processing behind in the embodiments of the invention 7 and arc discharges embodiments of the invention 8.As a result, confirmed that by AC impedence method this disk does not have electron conduction.Figure 23 represents the TOF-MS spectrum by the carbon dust (a) of arc discharge acquisition.As shown in figure 23, most of carbon dusts have 5500 or littler mass number, and promptly the carbon number amount is 500 or littler.Because the distance of the carbon-carbon bond in the carbon dust is less than 2 dusts, so the diameter of each carbon of this powder bunch is less than 100 nanometers.
Describe below and wherein use the embodiment of tubulose carbonaceous material as carbonaceous material
＜polyhydroxylated SWCNT material synthetic 1
The SWCNT material that preparation is refining, then in order to obtain polyfluoro SWCNT, in fluorine gas 250 ℃ of roastings 10 hours.Polyfluoro SWCNT is placed in the pure water, refluxed 3 days at 100 ℃, strong agitation so that replace fluorine atom with oh group, thereby produces polyhydroxylated SWCNT material, as the material of embodiments of the invention 9 simultaneously.
＜hydrosulphuric acid esterification SWCNT's is synthetic 〉
The polyhydroxylated SWCNT that produces with the method identical with embodiments of the invention 9 is placed in the oleum, stirs 3 days at 60 ℃, so that use OSO 3H group substituted hydroxy, thus the SWCNT material of hydrosulphuric acid esterification produced, as embodiments of the invention 10.
The Synthetic 2 of＜polyhydroxylated SWCNT material 〉
The SWCNT material that preparation is refining is handled through oxygen gas plasma then.Then, the atmosphere in plasma chamber replaces with hydrogen, and material is handled through hydrogen plasma, so that obtain polyhydroxylated SWCNT material, as embodiments of the invention 11.
The production of＜sample film 〉
Each of above-mentioned three kinds of materials is dispersed in the water,, suspension is filtered by swabbing action on the filter paper of 0.2 micron pore for deposit film on filter paper.Adjust the amount of the suspension that filters, formation thickness is 100 microns film.
The film that deposits on filter paper can easily be peeled off from filter paper.These films of Huo Deing are as the film of embodiments of the invention 9,10 and 11 like this.Filter with identical as mentioned above mode by the material of embodiments of the invention 10 is mixed the material that obtains with hydrosulphuric acid esterification fullerene derivate with 1: 1 weight ratio, form a kind of film, as embodiments of the invention 12.In addition, use identical as mentioned above mode to filter and do not contain substituent SWCNT material, form as a comparison
The film of embodiment 4.
The proton conductive of＜film is measured 〉
For the proton conductive of each film of measuring embodiments of the invention 9-12 and comparative example 4, the two sides of film remains between the aluminium foil of the disc-shape that is cut into 15 millimeters of diameters.Disk is placed between two electrodes, applies the alternating voltage that frequency range is 7MHz-0.01Hz (amplitude: 0.1 volt), measure the complex impedance under each frequency to film.Measurement is carried out in dry air.
The measurement result of the film among the comparative example 4 is described below, and the complex impedance of film is fixed under the low resistance, promptly since the electronic conductivity height of comparative example 4 SWCNT material in the said frequencies scope, do not change.Therefore, show that the film among the comparative example 4 can not be used as ion conductor.
The measurement result of the film among the various details embodiment 9-12.The complex impedance typical earth surface of the film of embodiments of the invention 10 is shown among Figure 24, with reference to Figure 24, a kind of still very smooth half-round curve that flattens is represented in impedance in the high-frequency region, the electricity of some charged particle is led in its expression film, the imaginary part of impedance raises rapidly in low frequency region, show along with moving closer to direct voltage, the obstruction of charged particle takes place between aluminium electrode and film.Obstruction about aluminium electrode in embodiments of the invention 10 and the charged particle between the film, the charged particle of aluminium electrode one side is an electronics, therefore, be apparent that the charged particle in the film is not electronics or hole, but ion, more clearly, be because film forming tubulose contains the proton that the structure of carbon derivative produces.About the film in embodiments of the invention 9,11 and 12, the film in the behavior of these films and the observed embodiments of the invention 10 is similar, although there is difference in the arc size between them.Therefore, shown film among the embodiments of the invention 9-12 can be ideally as the tubulose carbonaceous material derivative of proton conductor.
About above-mentioned impedance measurement, the proton conductive part 1 of film like proton conductor constitutes a kind of equivalent electric circuit, wherein, between first kind and second kind of electrode, form an electric capacity, in proton conductive between two electrodes part resistance is arranged, as discussed earlier in the embodiment institute similar determine also further represented in Figure 17 A.In addition, the hysteresis effect when electric capacity is represented protolysis (phase lag under the high frequency), resistance is represented the difficult parameters of protolysis.Measured impedance Z is represented with formula Z=Re (Z)+i-Im (Z).Studied the frequency dependence of proton conductivity part.
Based on the circular arc of high frequency side and the intercept of X-axis, can calculate the conductivity of above-mentioned charged particle.The conductivity of the film in the embodiments of the invention 10 is about 2 * 10 -5S/cm.The conductivity of the film in other embodiments of the invention differs from one another, and is as shown in table 3.
Table 3: the conductivity of proton conductor film of the present invention (25 ℃)
The film kind Conductivity (S/cm)
The film 9 of embodiments of the invention 2×10 -7
The film 10 of embodiments of the invention 2×10 -5
The film 11 of embodiments of the invention 7×10 -8
The film 12 of embodiments of the invention 3×10 -4
Obviously find out from table 3, make hydroxyl by OSO in the hydrosulphuric acid functional group that in the tubulose carbonaceous material, introduces 3When the H group replaced, the proton conductivity in the film was often bigger.Its reason is OSO 3The H group is than the easier ionization that causes hydrogen of hydroxyl.The result shows, contains oh group and OSO 3The tubulose carbonaceous material derivative aggregation of H group can show good proton conductive at normal temperature in dry atmosphere.

Claims (18)

1. proton conductor comprises: have the carbon bunch of at least one proton dissociation group, wherein this carbon bunch is to comprise the aggregation of the hundreds of of fullerene molecule to several thousand carbon atoms.
2. according to the proton conductor of claim 1, wherein, described carbon cocooning tool has a kind of structure that wherein has open end to the small part fullerene structure.
3. according to the proton conductor of claim 1, wherein, described carbon bunch comprises the carbon that combines bunch.
4. according to the proton conductor of claim 1, wherein, described proton dissociation group represents that with-XH wherein, X represents to have any atom or the atomic group of divalence, and H represents hydrogen atom.
5. according to the proton conductor of claim 4, wherein, described proton dissociation group with-OH or-YOH represents that wherein, Y is arbitrary atom or the atomic group with divalence, O represents oxygen atom.
6. according to the proton conductor of claim 5, wherein, described proton dissociation group be selected from by-OH ,-OSO 3H ,-COOH ,-SO 3H and-OPO (OH) 3In the group of forming.
7. according to the proton conductor of claim 1, wherein, in described carbon bunch, also introduce electron attractive group.
8. according to the proton conductor of claim 7, wherein, described electron attractive group is selected from the group of being made up of nitro, carbonyl, carboxyl, itrile group, haloalkyl and halogen atom.
9. according to the proton conductor of claim 1, bunch form by described carbon substantially.
10. according to the proton conductor of claim 1, also comprise polymeric material.
11. according to the proton conductor of claim 10, wherein, described polymeric material does not have electron conduction.
12. according to the proton conductor of claim 10, wherein, described polymeric material is to be selected from least a in polyvinyl fluoride, polyvinylidene fluoride and the polyvinyl alcohol.
13., comprise 50 weight % or polymeric material still less according to the proton conductor of claim 10.
14. according to the proton conductor of claim 10, wherein, described polymeric material comprises 3 weight % or polytetrafluoroethylene still less.
15. according to the proton conductor of claim 10, this conductor is that a kind of thickness is 300 microns or littler film.
16. according to the proton conductor of claim 1, wherein, described carbon bunch is a kind of tubulose carbonaceous material.
17. according to the proton conductor of claim 1, wherein, described carbon cocooning tool has diamond lattic structure.
18. according to the proton conductor of claim 1, wherein, the main axis length of described carbon bunch is 100 nanometers or littler.
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